The toxicokinetics and metabolism of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and their relevance for toxicity

This article reviews the present state of the art regarding the toxicokinetics and metabolism of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). The absorption, body distribution, and metabolism can vary greatly between species and also may depend on the congener and dose. In biota, the 2,3,7,8-substituted PCDDs and PCDFs are almost exclusively retained in all tissue types, preferably liver and fat. This selective tissue retention and bioaccumulation are caused by a reduced rate of biotransformation and subsequent elimination of congeners with chlorine substitution at the 2,3,7, and 8 positions. 2,3,7,8-Substituted PCDDs and PCDFs also have the greatest toxic and biological activity and affinity for the cytosolic arylhydrocarbon (Ah)-receptor protein. The parent compound is the causal agent for Ah-receptor-mediated toxic and biological effects, with metabolism and subsequent elimination of 2,3,7,8- substituted congeners representing a detoxification process. Congener-specific affinity of PCDDs and PCDFs for the Ah-receptor, the genetic events following receptor binding, and toxicokinetics are factors that contribute to the relative in vivo potency of an individual PCDD or PCDF in a given species. Limited human data indicate that marked species differences exist in the toxicokinetics of these compounds. Thus, human risk assessment for PCDDs and PCDFs needs to consider species-, congener-, and dose-specific toxicokinetic data. In addition, exposure to complex mixtures, including PCBs, has the potential to alter the toxicokinetics of individual compounds. These alterations in toxicokinetics may be involved in some of the nonadditive toxic or biological effects that are observed after exposure to mixtures of PCDDs or PCDFs with PCBs.     

加热方式与载气性质对废弃PVC热解脱氯的影响

为了使含氯废塑料能喷入高炉必须进行脱氯处理，研究了热解脱氯时加热方式及载气性质对脱氯率的影响。结果表明，用载气加热比直接加热效果好，用水蒸气作载气比用氮气作载气效果好。     

Origin attribution of polychlorinated dibenzo-p-dioxins and dibenzofurans in sediment and soil from a Japanese freshwater lake area through congener-specific data analysis

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/PCDFs) in sediment and soil from a freshwater lake area were congener-specifically determined. The obtained data were examined to estimate the major origins of these compounds, with the aid of principal component analysis (PCA). Four major principal components (PCs) were obtained, and three of them were attributed to PCDDs/PCDFs in the atmosphere, in a diphenyl ether herbicide and in pentachlorophenol, based on congener-specific comparisons with references. One PC remained unattributed. These four were interpreted as the major origins of PCDDs/PCDFs in the area. The relative influence of the origins was also investigated.     

Polychlorinated dioxin and dibenzofuran levels in the environment and food from the Republic of Bashkortostan, Russia

The paper summarises systematic 5-year monitoring of the environment, drinking water and food for PCDDs and PCDFs levels in industrial centres and in rural areas of the Republic of Bashkortostan, Russia. It also presents selected data on dioxin concentrations in gas emissions of toxic waste incinerators at chemical plants. The paper gives a comparative analysis of PCDDs/PCDFs daily intake by the population of industrial cities for Bashkortostan and for industrial countries of Europe and North America. The results show that PCDDs/PCDFs levels in the environment, drinking water and food in Bashkortostan are approximately equal to those in other industrial countries.     

Dioxin levels in the emissions from municipal waste incinerators in Taiwan

In this study, characteristics of dioxins emission from existing modern MWIs were evaluated via simultaneous sampling of flue gas and various types of fly ashes. Preliminary results showed that PCDDs congeners distributions were quite similar in flue gas and various types of ashes of both MWIs. PCDFs/PCDDs ratio in cyclone ash was lower than that in combustor ash or fabric filter ash excluding economizer ash of MWI-A. Similarly, PCDFs/PCDDs ratio in ESP ash was lower than that in boiler ash. PCDFs concentration was about 1.5 to 4.3 times higher than PCDDs concentration in flue gas of both MWIs. The mass balance factors of MWI-A (0.9 approximately 1.02) were clearly lower than that of MWI-B (7.71 approximately 15.63), indicating that de novo synthesis occurred under the operating conditions of ESP. In other words, MWIs equipped with ESP were less efficient in controlling PCDD/Fs emissions than that equipped with fabric filters.     

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in shellfishes from south coast of Korea

PCDDs and PCDFs were analyzed by high resolution GC-MS in two species of shellfish collected from southern coast of Korea. PCDDs and PCDFs were detected from all samples. Total concentration of PCDDs and PCDFs ranged from 4.4 to 19 pg/g wet weight and from 2.5 to 26 pg/g wet weight, respectively. By using a method of cluster analysis based on congener profiles, samples were categorized into two groups, "the urban group" and "the rural group". A tendency that TEQ levels of the urban group were higher than those of the other group was observed. Although a reliable source of dioxins in the samples was identified in this study, it was suggested that combustion sources are responsible for occurrence of dioxins in samples of both groups.     

A comparison of dioxins, dibenzofurans and coplanar PCBs in uncooked and broiled ground beef, catfish and bacon

The primary source of dioxins (PCDDs), dibenzofurans (PCDFs) and coplanar PCBs for the general population is food, especially meat, fish, and dairy products. However, most data on the levels of these chemicals is from food in the raw or uncooked state. We report here the effect of one type of cooking (broiling) on the levels of PCDDs, PCDFs, and coplanar PCBs in ground beef (hamburger), bacon and catfish. Samples of hamburger, bacon, and catfish were broiled and compared to uncooked samples in order to measure changes in the amounts of dioxins in cooked food. The total amount of PCDD, PCDF, and coplanar PCB TEQ decreased by approximately 50% on average for each portion as a result of broiling the hamburger, bacon and catfish specimens. The mean concentration (pg TEQ/kg, wet weight) of PCDDs, PCDFs, and coplanar PCBs, however, remained the same in the hamburger, increased by 83% in the bacon, and decreased by 34% in the catfish. On average, the total measured concentration (pg/kg) of the congeners of PCDDs, PCDFs, and coplanar PCBs increased 14% in the hamburger, increased 29% in the bacon, and decreased 33% in the catfish.     

Presence of dioxins in human follicular fluid: their possible stage-specific action on the development of preimplantation mouse embryos

Examination of human follicular fluid revealed the presence of polychlorinated dibenzodioxins (PCDDs) and dibenzofurans (PCDFs) at concentrations of approximately 1 pg/ml (0.01 pg TEQ/ml). To study their possible action, two-cell mouse embryos were cultured in the presence of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) at concentrations between 0.5 and 100 pM and evaluated at 24-h intervals for their development to the eight-cell and blastocyst stages. The percentage of eight-cell embryos exposed to TCDD at 1, 2, and 5 pM concentrations was significantly lower than that of controls. However, blastocyst formation of the surviving eight-cell embryos was accelerated, with the number of cells in the blastocysts increased in a dose-dependent manner. Findings suggest that PCDDs and PCDFs may be present in human reproductive fluid and may exert some stage-specific effects on early embryonic development.     

Interactions between 2,3,7,8-TCDD and PCBs as tumor promoters: limitations of TEFs

The assessment of the carcinogenic risk of polychlorinated dioxins (PCDDs), furans (PCDFs), and biphenyls (PCBs) by TEFs is hampered by species- and tissue-specific responses that cannot readily be explained by differences in the Ah receptor levels but may be due to events subsequent to ligand binding to the Ah receptor. Moreover, PCDDs and related compounds accumulate in the environment, in animal and human tissues as highly complex mixtures. Thus, comprehensive risk assessment should include all Ah receptor ligands and agents that modulate the Ah receptor-mediated responses. Tumor promoter studies with mixtures of PCDDs and halogenated biphenyls have shown additive, synergistic, and antagonistic effects. To analyse the interactions of TCDD and PCBs as tumor promoters in more detail, we established an in vitro assay, i.e., the enhancement (promotion) of malignant transformation of carcinogen-initiated C3H/M2 mouse fibroblasts after treatment with tumor promoters. The coplanar PCB 126, a potent Ah receptor agonist, and the diortho-substituted PCB153, to which no TEF value has been ascribed, are promoters of malignant transformation. A defined mixture of PCB126 and TCDD had an additive promoting effect, while PCB 153 antagonized the TCDD-mediated promotion. Thus, the TEF-approach may be insufficient to estimate the tumor-promoting activities of PCDDs, PCDFs, and PCBs in mammalian tissues in which diortho-substituted PCBs are greatly accumulated.     

Polychlorinated diphenyl ethers, dibenzo-p-dioxins, dibenzofurans and biphenyls in seals and sediment from the Gulf of Finland

Polychlorinated diphenyl ethers (PCDEs), 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) were analyzed in seals from the Gulf of Finland and in sediments from the Gulf of Finland and near Gotland. The sediments included one surface core from both sampling sites. The seal material consisted of 14 ringed seals and 6 grey seals that all were found dead and examined for pathology. The main aims were to scrutinize levels and patterns of PCDEs for the first time in seals from the Baltic Sea and to estimate whether chlorinated compounds mentioned have an influence on an exceptional high mortality that occurred among ringed seals in the Gulf of Finland in late 1991. The concentrations of 50 congeners of tetra- through deca-CDEs analyzed ranged from < 0.3 to 62 ng/g lipid weight (lw) in seal blubber, but in the sediments PCDEs were non-detectable (tetra- through hepta-CDEs < 0.1 ng/g dry weight (dw)). In ringed seals with good nutritional status, the concentrations of almost all PCDE congeners were greater in two adult females than in specimens of younger age groups. The concentrations of PCDDs and PCDFs as TCDD-equivalents exceeded those of the coplanar (non-ortho) PCBs in sediments, whereas non- and monoortho PCBs constituted greater toxic loads as those calculated for PCDDs and PCDFs in seals. However, the levels revealed do not explain the high mortality of ringed seals.     

Temperature determines the pattern of anaerobic microbial dechlorination of Aroclor 1260 primed by 2,3,4,6-tetrachlorobiphenyl in Woods Pond sediment

Reductive dechlorination of the Aroclor 1260 residue in Woods Pond (Lenox, Mass.) sediment samples was investigated for a year at incubation temperatures from 4 to 66 degrees C. Sediment slurries were incubated anaerobically with and without 2,3,4,6-tetrachlorobiphenyl (2346-CB; 350 microM) as a primer for dechlorination of the Aroclor 1260 residue. Dechlorination of the Aroclor residue occurred only in live samples primed with 2346-CB and only at 8 to 34 degrees C and 50 to 60 degrees C. The extent and pattern of polychlorinated biphenyl (PCB) dechlorination were temperature dependent. At 8 to 34 degrees C, the dechlorination resulted in 28 to 65% decreases of the hexathrough nonachlorobiphenyls and corresponding increases in the tri- and tetrachlorobiphenyls. At 12 to 30 degrees C, 30 to 40% of the hexa- through nonachlorobiphenyls were dechlorinated in just 3 months. The optimal temperature for overall chlorine removal was 20 to 27 degrees C. We observed four different microbial dechlorination processes with different but partially overlapping temperature ranges, i.e., Process N (flanked meta dechlorination) at 8 to 30 degrees C, Process P (flanked para dechlorination) at 12 to 34 degrees C, Process LP (unflanked para dechlorination) at 18 to 30 degrees C, and Process T (a very restricted meta dechlorination of specific hepta- and octachlorobiphenyls) at 50 to 60 degrees C. These temperature ranges should aid in the development of strategies for the enrichment and isolation of the microorganisms responsible for each dechlorination process. The incubation temperature determined the relative dominance of the four PCB dechlorination processes and the extent and products of dechlorination. Hence, understanding the effects of temperature on PCB dechlorination at contaminated sites should assist in predicting the environmental fate of PCBs or planning bioremediation strategies at those sites.     

高炉渣排氯能力的试验

 为找到合理有效的炉渣排氯制度,使得炉渣排氯能力最大化,在对高炉内氯元素进行热力学分析的基础上,研究了高炉渣的化学成分、温度以及恒温时间对排氯能力的影响。结果表明,高炉渣的排氯率随着炉渣碱度的提高而增加;其排氯率随温度的增加而降低;随[w(MgO)]的增加,其排氯率先增加后降低;随[w(Al2O3)]的增加,其排氯率先增加,当渣中[w(Al2O3)]超过16%时,其对炉渣排氯率的影响不大;随着恒温时间的延长,炉渣的排氯率降低。高炉在保证正常生产的前提下,应适当地提高炉渣碱度,降低高炉渣温度和增加出渣铁次数,[w(MgO)]和[w(Al2O3)]应保持在11.0%和16.0%左右,以提高炉渣的排氯能力,减少氯元素对高炉冶炼和后续设备产生的不利影响。     

Increased concentrations of octachlorodibenzo-p-dioxin in cases with breast cancer--results from a case-control study

Organochlorines are persistent and highly lipophilic environmental contaminants which bioaccumulate in the food chain. Some of these chemicals, 2,2-bis(p-chlorophenyl)-1,1,1-trichloroethane (DDT) and polychlorinated biphenyls (PCBs), have been suggested to be of significance in the aetiology of breast cancer. 2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) is an anti-oestrogen in animal studies and should be thus lower the risk of breast cancer. The other isomers of polychlorinated dibenzo-p-dioxins (PCDDs) or the chemically related polychlorinated dibenzofurans (PCDFs) have not been tested regarding carcinogenesis of the breast. The purpose of this study was to investigate whether PCDDs or PCDFs influence the risk for breast cancer. Consecutive patients who underwent surgery for a breast disease between 1993 and 1995 were recruited for the study. Cases were 22 patients with infiltrative breast cancer and controls were 19 patients operated for a benign breast disease during the same time period. Approximately 10 g of breast tissue free from tumour was taken from the specimen and frozen until analysis. Fat was extracted, cleaned and analysed with a high-resolution gas chromatograph coupled to a high-resolution mass spectrometer. Median concentrations of octachlorinated dibenzo-p-dioxin (OCDD) were 598 (170-14,880) and 396 (103-1,847) pg/g lipid in the cases and in the controls, respectively. In a multivariate logistic regression analysis controlling for other risk factors for breast cancer increased odds ratio (OR) was obtained for OCDD: 401-1000 pg/g lipid yielded OR 3.8, 95% confidence interval (CI) 0.4-39, > 1000 pg/g lipid gave OR 5.2, CI 0.4-72. When the lipid OCDD variable was examined as a continuous risk factor there was a 1.09 (9%), CI 0.95-1.25, increase in the adjusted OR for breast cancer per 100 unit (pg/g lipid) increase in OCDD. No differences were found between cases and controls for the other six tested PCDDs. Mean concentration of TCDD was in the cases 3.6 (1.0-7.9) and in the controls 3.3 (1.1-6.3) pg/g lipid. For PCDFs no significant differences were found between cases and controls. The results were not changed if oestrogen or progesterone receptor status, S-phase fraction and DNA ploidy were considered. Breast tissue concentration of OCDD was increased in cancer patients, whereas the concentrations of other PCDDs and PCDFs were equal in cases and controls.     

废弃聚氯乙烯热解脱氯的研究

高炉喷吹废塑料是20世纪90年代初由德国提出的处理废塑料的最佳方法，在国外高炉喷吹废塑料的实践中，含氯废塑料的处理一直是个难题，作对含氯废塑料的热解法脱氯进行了实验室基础研究。结果表明：在隔绝空气或用氮气保护的条件下，以一恒定的温度加热，氯脱除率超过90%，处理后的含氯废塑料可以直接喷入高炉。     

Estimated intake of PCDDs, PCDFs and co-planar PCBs in individuals from Madrid (Spain) eating an average diet

The estimated intake of PCDD/Fs and co-planar PCBs associated with an average diet consumed in Spain was investigated. The estimated total average intake for PCDDs and PCDFs from an average spanish diet was found to be 142 pg I-TEQ/day (2.4 pg I-TEQ/Kg b.w./day, for a 60 Kg person). PCDDs provided almost 80% of the total dioxin equivalents. This represents the upper bound estimate. If concentrations less than the LOD are taken as equal to zero, then the estimated average intake would be 81 pg I-TEQ/day which is the lower bound estimate. Data reported are in good agreement with those reported for other countries.     

从高氟氯烟尘中富集铟的研究

国内冶炼常规湿法流程锌浸出渣生产氧化锌脱氟氯时会产生大量的烟尘,其中含有锌、铅、铟、镉、氟、氯、砷等元素。研究了该烟尘富集铟、回收锌和铅以及处理氟、氯、砷等有害元素的工艺流程。结果表明,采取适当的工艺后可以回收烟尘中的有价金属。     

Trichloroethylene radicals generated by ionizing radiation. An EPR/spin trapping study

Trichloroethylene (TCE) was exposed in the presence of the spin trap N-tert-butyl-alpha-phenyl nitrone (PBN, 0.1 M) to ionizing radiation from two different sources in an attempt to determine the origin of the spin-trapped radicals generating the EPR spectra in precision cut liver slices. TCE samples were irradiated with 18 MeV electrons to a total dose of 1000 Gy in a linear accelerator (LINAC) or exposed to 60Co gamma-rays to total doses of 100 Gy and 1000 Gy. The results show that three PBN adducts were generated during the LINAC radiations. Two of these spin adducts correspond to the addition of carbon-centered radicals to PBN, and the third adduct is consistent with a decomposition product of PBN. The predominant carbon-entered radical yields a PBN adduct that is more stable, persists for over 24 h and has identical hyperfine coupling constants (aN = 1.61 mT, aH beta = 0.325 mT) to the PBN adduct obtained when precision-cut liver slices were exposed to TCE. Gamma radiation (100 Gy) of TCE yields PBN adducts with lower primary nitrogen hyperfine coupling constants (aN = 1.45 mT and aN = 1.54 mT). The results (gamma-radiation) suggest that the carbon-centered radical is formed on a single TCE carbon that is different than the predominant radical formed during LINAC radiations. This difference is confirmed by experiments using 13C-TCE. The results further suggest that, during gamma-radiation of TCE, the radicals are formed by dechlorination at the TCE carbon containing two chlorine atoms. The results obtained during LINAC radiations suggest that the predominant radical is formed by dechlorination at the TCE carbon containing a single chlorine and a single proton. In addition, it is possible that this radical is the initial TCE radical formed during exposure of liver slices to TCE.     

湿法炼锌体系铜渣脱氯试验及产业化研究

根据湿法炼锌体系流程中氯的来源和开路,进行了铜渣脱氯条件试验研究,条件试验优化为：浸出温度为70～75℃,反应时间为45～55min,铜离子浓度为1～2．5g/L,pH值为2．5—3．0,液固比为30：1,铜渣粒度为～120目占90％,在此条件下,脱氯率达到60．3％。并在优化条件的基础上,进行产业化运行,平均脱氯率可以达到47．02％。     

Microbial dechlorination of historically present and freshly spiked chlorinated dioxins and diversity of dioxin-dechlorinating populations

The ability of a microbial consortium eluted from dioxin-contaminated Passaic River sediments to dechlorinate polychlorinated dibenzo-p-dioxins (PCDDs) was investigated under methanogenic conditions. Aged 2,3,7,8-tetraCDD, which had partitioned into the microbial consortium from sediments, was stoichiometrically converted to tri- and monoCDD congeners. During dechlorination, dominant microbial activity within the consortium shifted from methanogenic to nonmethanogenic activity. Freshly spiked octaCDD was converted to hepta-, hexa-, penta-, tetra-, tri-, di-, and monochlorinated isomers, but the reaction stoichiometry was not determined. No methanogenic activity was observed, and the maximum yield of protein coincided with the production of less-chlorinated DD congeners. Two distinct pathways of dechlorination were observed: the peri-dechlorination pathway of 2,3,7,8-substituted hepta- to pentaCDDs, resulting in the production of 2,3,7,8-tetraCDD, and the peri-lateral dechlorination pathway of non-2,3,7,8-substituted congeners. Direct evidence of further lateral dechlorination of 2,3,7,8-tetraCDD was obtained from the historically contaminated incubations; no isomer-specific identification of triCDDs in spiked incubations was determined. Pasteurized cells exhibited no peri-dechlorination pathway, and triCDDs were the least-chlorinated congeners produced in these treatments. These results demonstrate that (i) both freshly spiked and aged PCDDs are available to microbial reductive dechlorination, (ii) the peri and triCDD dechlorinations are attributed to activities of nonmethanogenic, non-spore-forming microbial subpopulations, and (iii) the 2,3,7,8-residue patterns in historically contaminated sediments are likely affected by microbial activity.     

LNG用7％Ni钢快速回火工艺模拟

摘要：采用淬火膨胀仪模拟研究了LNG用7%Ni钢淬火后快速加热回火工艺,结合显微组织观察以及对回火冷却过程中膨胀曲线的分析,讨论了该工艺对钢中逆转变奥氏体含量及其稳定性的影响。结果表明,提高淬火终冷温度能显著增加组织中逆转变奥氏体的含量,且其在基体上的分布也更为均匀,但当淬火终冷温度提高至300℃时,淬火组织中残留了大量的残余奥氏体,经快速加热回火后虽然保留在组织中,但其稳定性较差,导致冷却后的最终组织中出现大量的岛状M/A。回火前的快速加热一方面抑制了残余奥氏体在加热过程中发生分解,同时也有利于碳原子在较短的时间内扩散至其中,因此不但能促进钢中逆转变奥氏体含量的增加,也有利于其稳定性的提高。